Drilling fluid



United States Patent 3,259,572 DRILLING FLUID Woodrow J. Dickson, La Habra, and Fred W. Jenkins,

This application is a division of Ser. No.47,386 filed August 4, 1960, now US. Patent No. 3,200,106.

This invention relates to branched polyalky-lene polyamines and to derivatives thereof. More particularly, this invention relates to said branched polyamines and to branched polyamine derivatives containing various groups, 'such as the oxyalkylated, acylated, alkylated, carbonylated, olefinated, etc., derivatives thereof, prepared by introducing such groups individualzly, alternately, in combination, etc., including for example, de rivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emulsions; as demulsifiers for oil-in-water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like; as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as antioxidants, gasoline stabilizers, fungicides, etc.; as flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphaltmineral aggregate compositions; as additives for compositions useful in acidizing calcareous strata of oil wells; as additives for treating water used in the secondary recovery of oil and in disposal wells; as additives used in treating oil-well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-inwater and water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing mud sheaths from newly drilled wells; as dehazing or foginhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing water-vapor impermeable paper board; as agents in parafiin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and antistalling agents for gasoline; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, for example, as mercerizing assistants, as wetting agents, as rewetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as anti-static agents for rugs, floors, upholstery,v

plastic and wax polishes, textiles, etc.; as detergents useful in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents useful in leather processes such as in flat liquoring, pickling, acid degreasing, dye fixing, and the like; as agents in metal ice pickling; as additives in paints for improved adhesion of primers, in preventing water-spotting in lacquer; as antiskinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink;as agents in the preparation of wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 24-D (Toxaphene), chlordane, nicotine sulfate, hexachloracyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulating building materials; and the like.

THE BRANCHED POLYAMINE The branched polyamines employed herein are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene i.e.

group per nine amino units present on the main chain, for example, 1-4 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units. Thus, these poly-amines contain at least three primary amino groups and at least one tertiary amino group.

These reagents may be expressed by the formula:

NH? ii KEN NH: y

RNH:

m R si- RN la? :Ln

where n is an integer, for example, l-20 or more but preferably l-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The preferred embodiments are presented by the following formula: 1

3,259,572 3 4 The radicals in the brackets may be joined in a head- 1-2 hours or longer, one can in many cases recover a to-head or a head-to-tail fashion. Compounds described second mole of water for each mole of carboxylic acid by this formula wherein n=1-3 are manufactured and group employed, the first mole of water being evolved dursold as Polyamines N-400, N-800, N-1200 etc. Polying amidification. The product formed in such cases conamine N-400 has the above formula wherein n=1. 5 tains a cyclic amidine ring, such as an imidazoline or These compounds may be prepared by a wide variety a tetrahydropyrimidine ring. Infrared analysis is a conof methods. One method comprises the reaction of ethvenient method of determining the presence of these anolamine and ammonia under pressure over a fixed bed groups. of a metal hydrogenation catalyst. By controlling the Water is formed as a by-product of the reaction beconditions of this reaction one may obtain varying tween the acylating agent and the branched polyamine reactant. In order to facilitate the removal of this water,

amounts of piperazine and polyamines as well as the to effect a more complete reaction in accordance with branched chain polyalkylene polyamine useful in this invention. This process is described in Australian applicathe principle of Le Chatelier, a hydrocarbon solvent which tion No. 42,189, new Australian Patent No. 233,766, forms an azeotropic mixture with water can be added and in the German Patent No. 14,480 (March 17, 1958) to the reaction mixture. Heating is continued with the reported in Chem. Abstracts, August 10, 1949, 14,129. liquid reaction mixture at the preferred reaction tem- These branched polyamines can also be prepared by perature, until the removal of water by azeotropic distilthe following reactions: lation has substantially ceased. In general, any hydro- CH: OH:

H: NH: NH:

Variations on the above procedure can produce other carbon solvent which forms an azeotropic mixture with branched polyamines. water can be used. It is preferred, however, to use an The branched nature of the polyamine imparts unusual aromatic hydrocarbonv solvent of the benzene series. Non properties to the polyamine and its derivatives. limiting examples of the preferred solvent are benzene, For the sake of brevity and to simplify presentation, toluene, and xylene. The amount of solvent used is a the invention will be described by the selection of one variable and non-critical factor. It is dependent on the branched polyamine to illustrate the reactions and uses size of the reaction vessel and the reaction temperature selected. Accordingly, a sufficient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction ACYLATION can also be removed by operating under reduced pressure. A wide variety of acylating agents can be employed. When operating with a reaction vessel equipped with a Acylation is carried out under dehydrating condition, i.e., reflux condenser provided with a water takeoff trap, water is removed. Any of the well-known methods of sufiicient reduced pressure can be achieved by applying acylation can be employed. For example, heat alone, a slight vacuum to the upper end of the condenser. The heat and reduced pressure, heat in combination with an 65 pressure inside the system is usually reduced to between azeotroping agent, etc., are all satisfactory. about 50 and about 300 millimeters. If desired, the water The temperature at which the reaction between the can be removed also by distillation, while operating under acylating agent and the branched polyalkylenepolyamine relatively high temperature conditions. is effected is not too critical a factor. Since the reactions The time of reaction between the acylating agent and involved appear to be an amide-formation reaction and the branched polyamine reactant is dependent on the a condensation reaction, the general temperature condiweight of the charge, the reaction temperature selected, tions for such reactions, which are well known to those and the means employed for removing the water from skilled in the art, are applicable. the reaction mixture. In practice, the reaction is con- Acylation is conducted at a temperature sufficiently tinned until the formation of water has substantially high to eliminate water and below the pyrolytic point ceased. Ingeneral, the time of reaction will vary between of the reactants and the reaction products. In general, about 4 hours and about ten hours. the reaction is carried out at a temperature of from 120 Although a wide variety of carboxylic acids produce to 280 C., but preferably at 140 to 200 C. excellent products, carboxylic acids having more than 6 The product formed on acylation will vary with the carbon atoms and less than 40 carbon atoms but preferparticular conditions employed. First the salt, then ably 8-30 carbon atoms give most advantageous products. the amide is formed. If, however, after forming the The most common examples include the detergent formamide atatemperature between 140-250 C., but usually ing acids, i.e., those acids which combine with alkalies not above 200 C., one heats such products at a higher 'to produce soap or soap-like bodies. The detergentrange, approximately 250-280 C., or higher, possibly up forming acids, in turn, include naturally-occurring fatty to 300 C. for a suitable period of time, for example, acids, resin acids, such as abietic acid, naturally occurring thereof (i.e. N-400). However, it is to be understood that such presentation is purely for illustration and the invention should not be limited thereto.

petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat difierent sources and are diiferent in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, proprionic, 'butyric, valeric, caproic, heptanoic, caprylic, nonacoic, capric, undecanoic, lauric, tridecanoic, myriatic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, anglic, teglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorrbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid pseudoeleostearic acid, and the like.

Carboxy-lic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hyd-roxyheptanoic acids, the hydroxy cap'rylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyr-istic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy s-tearic acids, the hydroxyoctadecenoic acids, for example, rioinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, the hydroxyelcosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxy'be'henic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and' the like.

Examples of the cyclic aliphatic carboxylic acidsare those found in petroleum called naphthenic acids, hydrocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fenchlolic acids, and the like. I

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xyleneic acids, 'alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like. s

Mixed higher fatty acids derived from animal or vegeta'ble sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oi-l, peanut oil, castor oil, seal oils, whale oil, sharkoil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed.

Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from parafiin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated napht-hoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc., derivatives), biphenyldicarboxylic acid, diphenylether dicanboxylic acids, d-iphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycanboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polyc-ar-boxylic acids are the dirneric, trimeric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glyccrides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides. I

Any alkenyl succinic acid anhydride or the corresponding acid is utilizable for the production of the reaction products of the present invention. The general structural formulae of these compounds are:

Anhydride CHr-O wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen,- sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper 7 limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in accordance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side react-ions to occur to some extent. Nevertheless, the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl succinic acid anhydride, is used herein, it must be clearly understood ,that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore. Non-limiting examples of the alkenyl succinic acid anhydride reactant are ethenyl succinic acid anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-Z-ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid; octenyl succinic acid anhydride; Z-methyl-heptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinic acid anhydride; nonenyl succinic acid anhydride; 2-propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; S-methyl-Z-isopropylhexenyl succinic acid anhydride; 1,2-dibromo-2-ethyloctenyl succinic acid .anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloroundecyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid; 3-ethy1-2-t-butylpe'ntenyl succinic acid anhydride; dodecenyl succinic acid anhydride; dodecenyl succinic acid; 2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized octadecenyl succinic acid; octadecyl succinic acid anhydride; 1,2-dibromo-2-methylpentadecenyl succinic acid anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,2-dichloro-2-methy1nonadecenyl succinic acid anhydride; 2-octy1dodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are diflicult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable herein. v

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cyclic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.,

R-CH-C CHFC V wherein P=branched polyamine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecularly with the branched polyamine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with the polyamine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced, i.e., by acylation. v

The moles of acylating agent reacted with the branched polyamine will depend on the number of acylation reactive positions contained therein as well as the number The following general procedure is employed in acylating. The branched polyamine is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from to 200 C. Where the formation of the cyclic amidine type structure is desired the maximum temperature is generally 180-250 C. and more than one mole of water per carboxylic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 3-A In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 1 mole (400 grams) of Polyamine N-400 is dissolved in an equal weight of xylene, i.e., 400 grams. 845 grams of oleic acid (3 moles) is added to the polyamine with stirring in about ten minutes. The reaction mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 54 grams (3 moles) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20mm. The product is a dark, viscous, xylene-soluble liquid.

Example 3A In the examples the symbol A identified the acylated branched polyamine. Thus, specifically 1-A, represents acylated Polyamine N-400, which polyamine is employed in all the reactions of the following table.

i i l 1 1 1 TABLE I.ACYLA'IED PRODUCTS OF POLYAMINE 10-40 OXYALKYLATION These branched polyamines can be oxyalkylated in Acid g g k2 i; of Water Remwed tlliehcogvtentiolgall manne, for example; by means of an oyamine a p aea 2 ene oxi e suc as et ylene oxide p-ro- N ame Grams N400 Mmes Grams 5 pylene oxide, butylene oxide, octylene oxlde, a higher M p m 1 7182 alkylene oxide, styrene oxide, glycide, methylglycide, etc., 182 or combmatlons thereof. Dependmg on the particular 12% application desired, one may combine a large proportion 3 95 of alkylene oxide, particularly ethylene oxide, propylene 38 10 oxide, a combination or alternate additions or propylene 4h 108 oxide and ethylene oxide, or smaller proportions thereof '32 in relation to the branched polyarnine, Thus, the molar 5 54 ratio of alkylene oxide to branched polyamine can range 311 90 within wide limits for example from a 1'1 mole ratio 4:1 5.9 106 r 53 to a ratio of 100011, or higher, but preferably 1 to 200.

52 For example, in dernulsification extremely high alkylene 1 40 oxide ratios are often advantageously employed such as 3 3 22 200-300 or more moles of alkylene oxide per mole of 112 20 branched polyamine. On the other hand, for certain ap- 0. i3 g; pl1cations such as corrosion prevention and use as fuel 0 0.66:1 4.1 74 011 additives, lower ratios of alkylene oxides are advang fit -QQ 0 g tageously employed, i.e., l/ 10-25 moles of alkylene oxide einic. per mole of branched polyamine. By proper control, de- 798 Z 58 sired hydrophilic or hydro hobic ro erties are im arted 94. dn 532 2.1 0.3 5.4 5 P p P 9 10-111... Alltenyl (C11) suc- 966 3:1 5.2 04 to the compos1t1on. As 1s well known, oxyalkylation ret' d ted under a w'd v f d't' 10-11,..- Anhydr1de(322) 044 21 38 ac 10118 are con uc 1 e ariety 0 con 11ons, 10 o. g 0.3 93.6 at low or high pressures, at low or high temperatures, in 3 f f 286 151 i p the presence or absence of catalyst, solvent, etc. For 12-141-" Oiticica 011' (920).-- 31 18 05:1 3( mstance oxyalkylation reactions can be carried out at E temperatures of from 80-200 C and r f f 610 m u 85 p essures 0 rom 324 1 1 it; 10 to 200 p.s.1., and times of from 15 min. to several 18 days. Preferably oxyalkylation reactions are carried out 1%.2 3.2 1 .2 13 at 80 to 120 C. and 10 to 30 p.s.i. For conditions of 98 36 oxyalkylation reactions see US. Patent 2,792,369 and 78 4 0 81 0 0 other patents mentioned therein. j g j "f5 Oxyalkylation is too well known to require a full i iiim uc Acid 990 3:1 3 54 discussion. For purpose of brevity reference is made l to Parts '1 and 2 of US. Patent No. 2,792,371, dated E E--- Teriilglthflhc (166)-- 23g 2 $3 40 May 14, 1957, to Dickson in which particular attention 17-11,-.- "-0001: s30 5, 6 m8 1s directed to the various patents which describe typical V oxyalkyla-tion procedure. Furthermore, manufacturers of 011141 substituent of 01116150 011 is the glyceride 01 1165516 acid: alkylene oxides furmsh extenslve i rmation as to the use of oxides. For example, see the technical bulletin H entltled, Ethylene Oxide, which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and The following table presents specific illustration of the large number of patents which deal with oxyalkylation compounds other than'N-400 and its derivatives. processes.

TABLE IA.-AOYLATED PRODUCTS Acid Mols of Acid Water Exam- Branched Per Mols 0i Removed ple Polyamine Branched Name Grams Polyamine Moles Grams 564 2:1 2.2 39.6 282 1:1 1.9 34.2 1,800 3:1 2.9 52.3 15 ,200 2:1 2.1 37.8 Alkenyl Succinic A11- 532 2:1

hydride (266) do 206 L;L Diglycolic (134) 134 1:1 1. 0 1s Mal Anhydride (98)-- 93 1:1 Naphthenic (33) Sunap- 330 1:1 2. 1 37.8

tic Acid B. Acetic 60 1:1 1. 1 19. 6 Diphenolic (286) 286 1:1 1.1 19.6 Stearic (284) 568 2: 1 1.3 32. 4 234 1:1 1.9 34.2 600 1:1 1.1 19.6 122 1:1 0.9 16.2 166 1:1 0.8 14.4 286 1:1 1.0 18.0 200 1:1 1.2 21.0 845 3:1 3.1 55.3 564 2:1 1.9 34.2 32-.43--. 202 1:1 1.0 18.0 33-11-..- 240 4:1 4.0 72.0

The symbol employed to designate oxyalkylation is O. Specifically 1-0 represents oxyalkylated Polyamine N-400.

In the'following oxyalkylations the reaction vessel employed is a stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means and the like which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 r.p.m. The branched polyamine, Polyamine N- 400, dissolved in an equal weight of xylene is charged into the reactor. The autoclave is sealed, swept with nitrogen, stirring started immediately and heat applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of the alkylene oxide is started and added continuously at such speed as it is absorbed by the reaction mixture. When the rate of oxyalkylation slows down appreciably, which generally occurs after about 15 moles of ethylene oxide are added or after about 10 moles of propylene oxide are added, the reaction vessel is opened and an oxyalkylation catalyst is added (in 2 weight percent of the total reactants present). The catalyst employed in the examples is sodium methylate. Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, oxyoctylation, oxystyrenation, and other oxyalkylations, etc., the catalyst is added at the beginning of the operation.

Example 1-0 Using the oxyalkylation apparatus and procedure stated above, the following compounds are prepared: 400 grams (1 mol) of Polyamine 400 are charged into a stainless steel autoclave, swept with nitrogen, stirring started, and autoclave sealed. The temperature is allowed to rise to approximately 100 C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been added over a one-half hour period. This reaction is exothermic and requires cooling to avoid a rise in temperature. The reaction mass is transferred to a suitable container. Upon cooling to room temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-0,

The same procedure as Examplel-O is used exactly except that 396 grams of ethylene oxide (9 mols) is added to 400 grams (1 mol) of Polyamine N-400. This reaction material is a dark viscous liquid at room temperature.

Example IO 12 tion is highly exothermic. The reaction mass now contains 1 mol of N-400 and a total of 22 mols of reacted ethylene oxide. I Example 1-0., A portion of the reaction mass of Example 1-O is transferred to another autoclave and an additional amount of EtO was added. The reaction mass now contains the ratio of 1 mol of N400 to 40 mols of E0.

Example 1-05 The addition of ethylene oxide to Example l-O, is continued until a molar ratio of 1 mol of N-400 to mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to Example 1-O is continued until a molar ratio of 1 mol of N-400 to 83 mols of EtO is reached.

Example 1-07 The addition of ethylene oxide to the Example l-O is continued until a molar ratio of 1 mol of N-400 to mols of EtO is reached.

Example 2-0 400 grams of N-400 are charged into a conventional stainless steel autoclave. The temperature is raised to 120 C., the autoclave is flushed with nitrogen and sealed. Then 290 grams of propylene oxide (5-mols) are added slowly at 120 C. A sample is taken at this point and labeled 2-0 This sample contains 5 mols of PrO for each mol of N-400. It is a dark very viscous liquid at room temperature.

Example 2-0 The addition of propylene oxide to 2-0 is continued as follows: The autoclave is opened and 35 grams of sodium methylate are added. Theautoclave is again purged with nitrogen and sealed. Propylene oxide is added carefully until an additional 290 grams have been reacted. A sample is taken at this point and labeled 2-0 This compound now contains 10 mols of propylene oxide for each mol of N-400.

Example 2O The oxypropylation of 2-0 is continued until an additional 638 grams of propylene oxide are reacted. A sample is taken at this point and labeled 2-0 2-0 con TABLE IL-OXYALKYLATED P R0 D UCTS [Moles of oxide/mole N400] Ex. EtO Wgt. PrO Wgt. BuO Wgt. Ih sical ro erties Moles (g.) Moles (g.) Moles (g.) y p p 1-01.... 5 2Z0 D kv' Log-"- 9 396 arDoiscous liquid. 1-0; 22 968 Semi-solid.

1,760 Solid. 3, 300 D0. 3,652 Do. 4,620 5 290 D Do.

ark vis u 10 580 D0. w snqmd 21 1,218 Do 43 2, 494 Do 71 4,118 Do 84 4,812 Do 6,380 Do. 5 360 Do. 10 720 Do. 38 2, 736 D0.

TABLE II.-Contlnued Ex EtO Wgt. PrO Wgt. BuO Wgt. Physical properties Moles (g.) Moles (g.) Moles (g.)

(I) 220 (II) 2, 320 Dark viscous liquid. 11 (I) 484 63 (II) 3, 654 Do. 17 (I) 748 88 (II) 3, 872 Do. 53 (I) 2, 332 19 (II) 1, 102 Semi-solid. 98 (I) 4, 312 95 (II) 4. 510 Dark thick liquid. 8 (II) 352 19 (I) 1, 102 Do. 22 (II) 968 39 (I) 2,262 Do. 18 (II) 792 96 (I) 5, 568 Do. 95 (II; 4, 080 105 (I) 6, Do. 55 (II 2, 420 5 (I) 290 Solid. 5 (III) 220 18 (II) 1, 044 5 (I) 360 Dark viscous liquid. 5 (II) 220 5 III) 290 25 (I) 1, 800 Do. 9 (I) 396 23 II) 1, 334 12 (II) 8 Do 19 (III) 836 19 (II) 1, 102 39 (I) 2, 808 Do (III) 1,980 75 (I) 4,350 10 (II) 7 Do. Octylene oxide 5 moles, 635 g. Do. Octylene oxide 8 moles, 1,016 g. Do. I Styrene oxide 4 moles, 480 g. Do. Styrene oxide 7 moles, 840 g. Do. Epoxide 201 1 mole, 280 g. Solid.

ACYLATION THEN OXYALKLATION Prior acylated branched polyamines can be oxyalkylated in the above manner by starting with the acylated M015 Oxide perMol 30 branched polyamine instead of the unreacted amine.

Branchfid Branched Polyamim Non-limiting examples are presented in the following ample Polyamme Properties tables. The symbol employed to designate an acylated, Eto Pro Buo oxyalkylated branched polyamine is A0. Specifically 1A O represents acylated, then oxyalkylated polyiifiuiif 3 amine N-400.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TABLE IIA.--OXYALKYLATED PRODUCTS Example 3A O For this example an autoclave equipped to handle alkylene oxides is necessary. 1156 grams (1 mole) of 3 A (N400+3 moles Oleic Acid minus three moles H 0) are'charged into the autoclave. Following a nitrogen purge and the addition of 120 grams of sodium methylate, the temperature is raised to 135 C. and 5683 grams of E0 (98 mols) are added. At the completion of this reaction, 2024 grams of PrO (46 moles) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent.

50 Example 5A 0 For this example a conventional autoclave equipped to handle alkylene oxides is necessary. 946 grams of 5-A (N-400+3 moles lauric acid minus 3 moles H O) are charged into the autoclave. The charge is catalyzed With Octylene Oxide, smols 100 grams of sodium methylate, purged with nitrogen and Styrene Oxide, 10 mols Do.

Epoxide 201, 2m01s heated to 150 C. 480 grams (4 moles) of styrene oxide D0: are added and reacted for 24 hours with agitation. The 33: resulting product is a dark extremely viscous fluid. Do. 38: V g Example 7A O 0. For this example a conventional autoclave equipped Do: 5 to handle alkylene oxides is necessary. 1314 grams of B3: 7-A (N-400-l-4 moles palmitic acid minus 6.2 moles 3: H O) are charged into the autoclave. Following the ad- Bg. dition' of 120 grams otf sodium methylate and a nitrogen purge, the mass is heated to 135 C. 660 grams of EtO g2: (15 moles) are added and the reaction proceeded to 3g: completion. Then 1440 grams of B110 (20 mols) Do. are added and again the reaction proceeded to compleo ciiiii 3233', i6 1351s i5 5. tion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent.

These reactions are summarized in the following table:

TABLE III.ACYLATED, OXYALKYLATED N400 [Moles of oxide/mole of reactant] EtO PrO BuO Ex. Physical Properties Moles Wgt Moles Wgt. Moles Wgt. (a) (e) (a) 1A1O1.. 42 (II) 1, 048 78 (I) 4, 524 Dark, viscous liquid. l-A1O1 8 (II) 352 59 (I) 3, 422 D0. 1A40z 8 (III) 352 18 (II) 1,044 15 (I) 1,080 Do. l-A4O|.- 23 (III) 1,018 47 (I) 2, 726 10 (II) 720 D0.

(I) 528 22 (II) 1, 276 Solid.

528 29 (I) 1, 682 Dark, thick liquid. 2, 024 98 (I) 5, 683 0. 176 Solid. 4"A1OI-- 5 290 D0. 4-A1Os 3 (I) 132 3 (II) 174 D0. 5A1O1 6 432 D0. 5A1Oz. '2 (I) 116 3 (II) 216 D0. 5-A1O:. Styrene oxide 4 moles, 480 grams Dark. viscous liquid:

Octylene oxide 5 moles, 635 grams o. 15 (I) 660 20. (II) 1,440 Dark, thick liquid. 10 (II) 440 30 (I) 1, 740 D0. 109 (II) 4, 796 210 (I) 12, 180 D0. 23 (I) 1,018 18 (II) 1, 044 3 (III) 216 D0. 23 (I) 1,018 26 (II) 1,508 Do. 9A:1O:.- 30 (II) 1,584 78 (I) 4,524 Do. 11-11101- 32 (I) 1,408 (II) 1,334 Solid. 11-11101.-- 13 (I) 572 49 (II) 2,842 Do.

The following table presents specific illustration of Example 2-O A compounds other than N-400 and its derivatives.

TABLE III-A.ACYLATED, OXYALKYLATED BRANCHED POLYAMIN Mols of Oxide Per Moi oi Reactant Example Physical Properties EtO PrO BuO 18A101 5 Dark. viscous liquid. 18-A1O2 10 (II) 60 (I) Do. 18-240 Do. 18-11104 5 (III) 40 (II) 10 (1) D0. 18-Az05.---- Styrene oxide, 4 mols 22-11101 3 (I) (II) D0. 25-11101" 2 (I) Do. 25-A1 Octylene oxide, 5 mols 26-1540 10 (I) 80 (II) 10 (III) D0. 26A1O 2 (I) 2 (II) Do. 26-11103" D0. 27-A101-- 3 (II) 8 (I) 1 (III) Do. 27-11 01 5 Do. 27-A103 D0. 27-A1O1 Do. 28A101 60 (II) 5 (III) 26 (I) Do. 31-11 01. 1 D0. Lil-A10 5 Do. 3 D0.

Epoxide 201, 1 mol Styrene oxide, 10 mols OXYALKYLATION THEN ACYLATION Example 1O A One mole of 1-0 (620 grams) is mixed with three moles of acetic acid (180 grams) and 400 ml. of xylene at room temperature. The temperature is raised slowly to 120-130 C. and refluxed gently for one hour. The temperature is then raised to ISO-160 C. and heated until 3 moles of water and all of the xylene are stripped 01f. The dark product is water-soluble.

One mole of 2-0 (2894 grams) is mixed with one mole of palmitic acid (256 grams) at room temperature. Vacuum is applied and the temperature is raised slowly until one mole of water (18 grams) is removed. This product is a dark viscous liquid.

Example 6-O A One mole of 6-0 (7450 grams) is mixed with 500 grams of xylene and heated to C. One mole of diglycolic acid (134 grams) is added slowly to preventexcessive foaming. The temperature is raised to -150 C. and held until one mole of water has evolved. This product is the diglycolic acid fractional ester of 6-0 A white precipitate 'Iorms during this reaction which can be removed by filtration. Analysis shows the precipitate to be sodium acid diglycollate, a reaction product of the catalyst and diglycolic acid. The filtered product is a dark viscous liquid at room temperature. I

Table IV contains examples which further illustrate the invention. The symbol employed to designate oxyaikylated, acylated products is 0A.

TABLE IV.--OXYALKYLATED, THEN ACYLATED BRANCHED POLYAMINE N400 Acylating agent Water removed Physical Ex. properties Moles oi Wgt., Wgt. Name acylating grams Moles (g) agent 101A-- Acetic 3 180 3 54 Dark liquid. 1-0:A.- Olei 1 282 1 18 Do. 1O:A.- Stearic 2 568 2 36 Solid. 2-01A-- Laurie 1 200 I 18 Dark liquid. 2-0;A. Myristie--- 2 457 2 36 Do. 2-O4A-- Palmitim--- 1 256.4 1 18 Do. 4-01 Oleic 2 564 2 36 Solid. 4-0 Ricinoleic.-- 1 298.5 1 18 Dizirlfnd 5-01A-- Abietlcacid. 1 302.4 1 18 Dar solid. 6-0 T311011-.- 1 1 18 Dark liquid. 6-01A.- Llnoleic. 1 280.4 1 18 Do. 6-0;A Oieic 2 564 2 36 Do. 6-0;A.- Maleic an- 1 98 1 18 Viscous hydride. liquid. 6-0 A-- Diglyeolic.-- 1 134 1 18 Do. 7O1A- Laurie 2 400 2 36 Dlarlr d i 8-O1A.- Stearic 1 284 1 18 S011 The following table presents specific illustration of compounds other than N-400and its derivatives.

TABLE IV-A.XYALKYLATED, THEN ACYLATED BRANCHED POLYAMINE Water Re- Mols of moved Physical Example Name Aeylating Wt. in Proper- Agent Grams ties Mols Wt.in Grams Ill-03A--- Stearic 1 1 18 Solid. 11-0111--- Laurie 2 400 2 36 Viscous liquid. 11-0gA--- Dlglycolic.-- 1 134 l 18 Dark liquid 1201A Maleic an- 1 98 Viscous hydride. liquid 13-0111-.- Oleic 2 1 18 D0. l t-01A--- Linoleic.- 1 280.4 1 18 Do. 15-01A--- Tall oil 1 175 1 18 p0. 16-0111--- Abieticaeid- 1 302 1 18 SOlld. 17-011---. Ricinoleic.-. 1 298 1 -18 Viscous liquid 18-OA Oleio 2 564 2 36 D0. 20O|A Palmitic 1 256 1 18 Solid. 20-0 A--- Myristie. 2 457 2 36 Do. 21-0111--- Laurie 1 200 1 18 Do. 21-0A Stearic- 2 568 2 36 Do.

22-O1A--- Oleic 1 282 1 18 Viscous liquid 23-0 A Acetic 1 60 1 18 Do. 24-03A--- Diphenolic 1 286 1 18 130. 25-0111--- Tereph- 1 166 1 18 Solid.

thalic. 25-04A--- Naphthenic. 2 330 2 36 Viscous liquid. 25-0 A do 1 330 1.9 34 Do. 26-01A--- Beuzoic 1 122 1 18 Do. 26-0111--- Laurie 1 200 1.8 32 Do.

HEAT TREATMENT OF OXYALKYTQATED PRODUCTS The oxyalkylated products described herein, for example, those shown in Table II relating to oxyalkylated branched polyamines and those in Table HI relating to oxyalkylated, prior acylated, branched polyamines can be heat treated to form useful compositions.

In general, the heat treatment is carried out at 200- 250 C. Under dehydrating conditions, where reduced pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example ISO-200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/or reduced pressure can be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulas for the reason that the structures are subject to a'wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is effected by heating same at elevated temperatures, generally in the neighborhood of ZOO-270 0., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile dis-v tillate usually contains water formed by reaction. The Water can be separated from such condensed distillate by usually a significantly higher temperature.

any suitable means, for instance, distilling with xylene, so as to carry over the water, and ubsequently removing the xylene. The dried condensate is then returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a high-boiling solvent, which is permitted to distill in such a manner as to remove the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the orginal reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the Water of reaction is removed from the combining mass. Polymerization can be effected without the use of catalysts in some instances, but

such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and The use of catalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. The symbol used to designate a'heat treated oxyalkylated polyamine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material and a temperature of 225-250 C. are employed.

Example 1-O H A conventional glassresin vessel equipped with a stirrer and water trap is used. Five hundred grams of 1-0; are charged into the above resin vessel along with five grams of CaC-l The temperature is raised to 225-250 C. and heated until grams of water (2.8 mols) are evolved. This process takes 7.5 hours of heating. The product is an extremely viscous material at room temperature. However, upon warming slightly this produc dissolves easily in water. I

Example 2O H The process of the immediately previous example is repeated using 2-0 but substituting sodium methylate for calcium *chloride. The product is a dark, viscous, water-soluble material.

Example 6O H The process of Example 1-O H is repeated using 6-0 but substituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (l) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED POLYAMINE N400 All oi the above products are dark, viscous liquids.

The following table presents specific illustration of compounds other thanN-400 and its derivatives.

TABLE VA.HEAT TREATED (l) OXYALKYLATED AND (2) ACYLATED. OXYALKYLATED BRANCHED POLYAMINE Example Wt. of Water Mols of H Time in Removed Removed Hours 10-0211"--. 31 1. 7 7. 11-011 61 3. 4 8. 0 12-O1H 33 1.8 6.8 13-0 63 3. 5 8.0 14-011 47 2. 6 8. 5 15-0111--." Sodium meth- 27 l. 5 7. 5

ylate. 16-O Ff CaC 5O 2. 8 8. 0 20-01H CaOH--- 54 3. 0 8. 5 21-0111---" Iron- 40 2. 2 10.0 22-0 do 56 3. l 9. 3 23-0111 dn 63 3. 5 8. 0 25-0 do 58 3. 2 7. 5 18-A201H..-- d0 29 l. 6 8. 5 18-A1O do 50 2.8 7. 5 25-.Ar0zH--- NaOH 29 1. 6 8.5 26-A1O-Fl' n 63 3. 5 8. 0 27-ArOaH--- 33 1. 8 6. 8 ii-A KO'FI 27 l. 5 7. 5 33-A10-IT do 50 2 8 8. 0

All of the above products are dark, viscous liquids.

ALKYLATION Alkylation relates to the reaction of the branched polyamine and derivatives thereof with alkylating agents.

'Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethylhexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-anethyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-chlorowax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and the branched polyamine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. It'is preferable to carry out the reaction at temperatures of between about 100 and about 250 C., preferably between about 140 C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for example, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines, alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the alkyl halide reactant and the branched polyamine reactant in a hydrocarbon solvent under reflux conditions. The aromatic hydrocarbon solvents of the benzene series amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and the branched polyamine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued untilno more hydrogen halide is formed. In general, the time of reaction will vary widely such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and the branched polyamine results in the formation of products where the alkyl group of the alkyl halide has replaced a hydrogen atom attached to a nitrogen atom. It is also conceivable that alkylation of an alkylene group of the branched polyamine can occur. However, the exact composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of Polyamine N-400, a mixture of mono-, diand triand higher N-alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in different molecules of the branched polyamine.

Thus, the term Alkylation as employed herein and in the claims includes alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the branched polyamineat the desired ratio in the presence of one equivalent of base for each equivalent HCl given off during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, no base is added. 1

The following examples are presented to illustrate the alkylation of the branched polyamines.

Example 5-K;

One mole of each of the following: tetradecylchloride, Polyamine N-400, and sodium bicarbonate are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a condenser reflux take-01f for removal of water from the reaction as it is evolved in an azeotropic mixture of Water and'a hydrocarbon solvent. The reflux take-off isfilled with xylene. The stirred reactants are heated to about C. whereupon an exothermic reaction causes the temperature to rise to about C. The reaction temperature is then increased to160 C. and held there for two hours. Then, xylene is added to the reaction vessel in an amount suflicient to cause a xylene reflux to take place at a temperature of l70 C. The reaction is continued for six hours or until the theoretical amount of water is removed. Thereupon, an equal volume of xylene is added to the reaction mixture and the resultant solution is filtered. This filtrate is then evaporated under reduced pressure to yield a dark amber oil. No halogen was present in this product as evidenced by a negative Beilstein copper wire test.

Example 5K X The above reaction is repeated except that no sodium bicarbonate is employed in the reaction. The reaction product contained chlorine.

The reactions shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two ways( 1) in the presence of base as in 5-K to yield the halogen-free al-kylation product Table VI and (2) in the absence of base to yield halogen containing products in the manner of 5-K X Table VII.

The alkylated products of this invention contain pri- TABLE VI.--Continued mary, secondary, tertiary, and quaternary amino groups. 7 By controlling the amount of alkylation agent employed 1 R2310, lA/Iolest ofAllkyflli hyslcal and the conditions of reaction, etc., one can control the $233 f fig f ag 225: type and amount of alkylation. For example, by reaction Derivatives less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen bonded hydro- 34:1 z-etr i t-nex i chlo- 311 vr cm gen present on the molecule and by exhaustive alkylation 346 5:1 in the presence of sufiicient basic material, one can form if M 7:1 S 130. more highly alkylated compounds. chmflde-mg The moles of alkylatin'g agent reacted with the branched t? "go 3:1 S go. polyamine will depend on the number of alkylation reac- Tem':1ecy1 chloride f3 g ttve positions contained thereln as well as the number of 5X 6 8 spam. moles of alkylating agent one wishes to incorporate into 2;} 5 the molecule. Theoretically every hydrogen bonded to a 5 -K: O t de y c r m 1:1 nitrogen atom can be alkylated. We have advantageously an 3:1 5% reactedl-IO moles of alkylatrng agent per moles of Poly- 3- do In 4 1 Do. amine N400, but preferably 16 moles. With Polyamine Benzylc Mme N-800 and N-1200, twice and three times as many moles 1 5-? 2 5:1 801%. of alkylatin-g agent can be employed respectively, i.e., with 1K: Allyl zghlnride v fg Polyamme N-800, 1-20 moles, preferably 1-12; w1th 84? d Polyamine N-1200, 1-30 but preferably 1'18. Optimum 3% 3: alkylation will depend on the particular application. 3:5 Dodgrenylchlorlden 1:1 S 130. In addition, the alkyl 'halide may contain functional n 3, 5, I groups. For example, chloroacetic acid can be reacted 2 5: with the branched polyamines to yield a compound con- IO-KI nggifiylbenzyl cmo' sohd' taining carboxylic acid groups 13: #1 3 PN CHzCOOH 11-11, l,4-dlchlorobutene-2 1E2 vilsigolilisi wherein is the residue of the polyarnine. 3 3;; 58: In addition, the branched polyamlne can be alkylated lz-Ki 1,4-xyly1ene diehlo- 1:2 Do. with an alkyl halide such as alkyl chloride and then reis; 3:1 acted with chloroacetic acid to yield an alkylated poly- 1%? my h l 11 5:1 130. amine containing carboxylic acid groups s yet 3: 0 1'01]; -do 5:1 Semi- H solid (0 uHzsN-) r-P-(O H10 0 H) Behzylchloride 8: 1 801111:

M h 1 hi rid en Li uid. The symbol employed to designate an alkylated poly- Di1 1th1s3lra:e 4:1 Do. amine is K." Where the product lS a salt or a quaternary I Ethylene dichloride 211 4 h b 1 KX u i llquld. t e y 0 1S 5-0pm: 1,4 dichlorobutene-2 4.1 Do. TABLE VL-ALKYLATED PRODUCTS l-MhK Dodecylchlonde-mg 7-1 0 K- -.Am lb'o lde 4:1 Viscous Ratio, Moles ofAlkyl- Physical n Y m liquid, Ex- A y fl s ati g Agent/Mole of Proper- 4OHK 1,4-xylylene dichlo- 3:1 Do.

Agent Po1yamlne400 or ties e,

D riv w 6-O1HK Methyl chloride 6:1 Liquid. 7-ArOzHK...- Dlehlorodiethylether. 4:1 vilsicoti s1 V 11 1-K1 Butyl chloride 1:1 Vilseous1 11 ,0 HK (10 4:1 in,

lqlll 3:1 D0. 5:1 D0.

38' The following table presents specific illustration of com- :1

pounds other than N-400 and its derivatives.

TABLE VI-A.ALKYLATED PRODUCTS Example Ratio, Mols of Branched Alkylating Agent Per Physical Polyamme Alkylating Agent Mol of Branched Prop- Polyamine or erties Derivatives 2:1 Viscous liquid 3:1 Do. 5:1 D0. 1: 1 Semisolid. .-d0 3:1 Do. Allyl chloride 1:1 Viscous llqui .d0 2:1 Do. do 3:1 Dc. Butyl chloride 1:1 Do. do 3:1 Dot 5:1 Do. 6:1 Do. 3:1 D0. 1:1 D0. 2:1 D0. 1:1 D0. N-1200- Allyl chloride 2: 1 Do. N-1200. Octadecyl chloride-.. 3:1 Do. N1200 n-Amyl bromide- 1:1 Do. N-1200- Benzyl chloride- 2:1 Do. N1200. Dichloropentane 1:1 Do. N1200 Methyl chloride 1:1 D0.

The following table presents specific illustration of compounds other than N400 and its derivatives.

TABLE VIL-SALT AND QUATERNARY PRODUCTSv OF ALKYLATED N400 AND DERIVATIVES Ratio, Moles of Physical Ex. Alkylating Agent Alkylating Agent] of Prop- Poiyamine N-400 erties 5 or derivative TABLE VIIA.SALT AND QUATERNARY PRODUCTS OF Butyummdej-"m 3331; ALKYLATED BRANCHED POLYAMINE AND DERIVA- -rmr (in 3:1 Do. TWES l-R'JC dn 6:1 Do. 2-1 1 n-Amyl bromide 2:1 Do. 10 2-170! do 4:1 D0. Ratio of Alkylatlng Physical Z-Y- do 6:1 Do. Example Alkylating Agent Agent/of Qoiyamine Propers-mx... zet lyl-hexyi chlo- 3:1 or Derivative ties 1'1 6. 3.1m: (in 5:1 34cm fin 7:1 Ethylene dichloride. 2:1 Solid. 4-K1X Dodecyl chloride 2:1 nkmyl bromide 3:1 Do. Dichlorodiethyl- 4:1 Do. 441.3: (in 3:1 ether. 4-1233! dn 5; 1 Dirnethyl sulfate-.- 3:1 Do. 5-K:X.. Tetradecyi chloride. 1:1 Methyl chloride..." 2:1 Do. 1,4-xylene dlchlo- 5: 1 Do. 4m: :10 3:1 ride. 54(1)? (in 6:1 Dodecyibenzyi 8:1 Semi; 6-K|X..---- Octadecyi chloride 1:1 chloride. solid. 5407K (in 3:1 1,4-dieh1orobutene-2. 3:1 Do. 6-10)? (in 4; 1 Benzyl chloride. 4:1 Do. 7KrX Benzyl chloride--. 1:1 Methyl chloride 3:1 Do. Ethylene dichloride. 2:1 Do. FIT-Y do 5:1 Dodecyl chloride-.. 1:1 0. 7 w.Y do 3: 1 Dichlorodiethyl- 1: 1 Solid. 8K|X Allyl chloride 3:1 ether. p Benzyl chlor1de 3:1 -Do. 3453: do 4:1 do 2:1 Do. 8 do 6:1 do 1:1 Do. 9-K1X Dodecenyl chioride 1:1 Methyl chloride--- 2:1 go. i I 0. 2 940K an 3:1 -do 3:1 Do. 9467? do :1 Dlchlorodiethyl- 3:1 D0. 10-K1X Dodecylbenzyl 2:1 ether. 5 chloride. 2:1 Do. 10- 4:1 1:1 Do. 5 104m n 5:1 11K1X 1,4-dichlorobutene-2. 1:2

4m: (in 2:1 11- dn 3:1 I 12-K;X Lt-ylylene dichlo- 1:2 0. i M ii ALKYLATED THEN ACYLATION 4m: (In o. 13-K|X Dichlorodiethyl- 1:1 D0. a? 1 3:1 Seam The alkylated material prepared above can be further 501i treated with acylating agent where residual acylatable an? d 5 1 sohd amino groups are still present on the molecule. The acyla- 02K Benzylchlofiglen tion procedure is essentially that described above wherein fifiag f flfgfg 23% 12,23 carboxyiic acids react with the alkylated polyamine under liq dehydrating conditions to form amides and cyclic amidines. 2:1 ffifg ii figfigfiggfi 5 The product depends on the ratio of moles of water re- Dodecyl moved for each carboxylic acid group, i.e., 1 mole water/ LAIDKXU mmylbrommmun v 1 mole carboxyli'c essentially amides; more than 1 mole liquidwater/1 mole carboxylic acid group, essentially cyclic 315 dichlo' amidines, such as imidazolines. 6-0: KX----- M y chloride-n 611 Such compounds are illustrated in the following table 4: 7 g fi g 1 The symbol employed to designated alkylated acylated II-AIOIHKX- products is KA and acyiated, alkylated, acylated products is AKA.

TABLE VIIL-ACYLATED, PRIOR ALKYLATED BRANCHED POLYAMINES Moles of Aoylat- Moles Ex. Acylatlng Agent ing A cut/Mole Wgt. Water Physical of 406 01' Removed Properties Derivative 1-12: A Ohio 2 564 3. 1 Viscous liquid. 2-K1A Stearie 3 852 3.0 Solid. 3-K-A Laurie 2 400 2.8 Viscous liquid. 4-K. A Pqim1t1c- 3 769 4. 1 Do. 5-K1A DLmeric 1 600 2.2 Do. K9. Alkenyl (Cn) 1 266 0.5 Solid.

succrmc anhydride. 7-KzA Olerc 1 282 1 7 Viscous liquid. 94? A d0----. 2 564 3. 1 Do. 11-16 A Laurie 2 400 2. 8 D0. lit-Kai.--" Rielnoleic 2 598 3.0 Do. 1-0:KA Olelc 1 282 1.5 Do. 3-AaKA1. A1keny1 (0n) 1 266 Solid.

sucemlc anhydride. 3-A3KA1 0le1e 1 282 1. 5 Viscous liquid.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TAB LE VIII-A.-AGYLATED, PRIOR ALKYLATED BRANCHED PO LYAMINE Mols t Aoylating Wt. of M015 0! Physical Example Acylating Agent Agent/M010! Acylatlng Water Proper- Polyamine or pent Removed ties Derivative sed 14-113 A Lam-i0 1 200 1. 1 Solid. 3 894 3.0 Do. 1& A 2 564 3. 5 Do. 17-K1A Palmltlc 2 512 2.0 Do. 18-1.; earlc 1 568 l. 0 D0. IO-O-R'A Oleio 1 282 1. 0 D0. -OAKA T innlnln 2 560 2, 0 D0, 26A|O;KA Acetic 1 60 1.5 Do. 11O,AKA Diglycollc 1 134 1.0 Do. 14O:HKA Maleicanhydride- 2 196 Do. 25A1O1HK A Oleic 1 282 -1.5 Do.

OLEFINATION The reaction proceeds smoothly without the aid of a (Olefination relates to the reaction of the polyamine and derivatives with olefins) The compositions of this invention, including the .branched polyamine itself as well .asvreaction products thereof containing active hydrogens, can be reacted with unsaturated compounds, particularly compounds containing activated double bonds, so as to .add the polyamine across the double bonds as illustrated herein:

(ll) PNH cH|=0HcoB PN-CHr-G O Ha -O R Where one or more active hydrogens are present at another reactive site, the following reaction could take place:

0 o R O (J-CH-C Ha-NP (N-CBk-CH-iii O R)! The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner and Zook (Wiley, 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives thereof including the following-acrylonitrile, acrylic and rnethacrylic acids and esters, crotonic acid and esters, cinnamic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, the polyamine and derivative thereof containing active hydrogens can be used to prepare telomers of polymer prepared from vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is f and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no water is eliminated.

The reactionis relatively simple, as shown by the following example: I

Charge 400 grams of N-400 (1 mol) into glass resin apparatus. Care should be taken that the N-400 is watercatalyst. Warm gently to -100 C. and stir for one hour.

Example 6-U To 800 grams of N-400 (2 mols) in 800 grams of xylene, add 124 grams of divinyl sulfone (1 mole) at room temperature. This reaction is exothermic and care must be taken to prevent an excessive rise in tempcrature which would cause cross-linking and insolubilization.

Example 3-OiU Same reactions as Example l-U except that 1 mol of TABLE IX.OLEFINATION .Moles of Olefin} Compound Olefin Mole oi Polyamine Time Tempera- N-400 or Polyamine ture, C. N-400 Derivative 1-U Acrylonitrile .l/l 80-100 2-Ur..- Methyl meth- 1/1 80-100 acrylate. 2-U, -do- 3/1 s0-100 3-U Ethyl emna- 1/1 120 mate. Ethyl crotonate. 1/1 120 Di-actyl male- 1/1 150 a e. Divinyl sulione. 1/2 Styrene 1/1 90 ---do 3/1 90 Lauryl meth- 3/1 120 acrylate. Divinyl sulfone' 1/2 90 Methyl meth- 1/1.

aorylate. Divmyl sulfone- 1/2 90 Aerylonitrile 2/1 70 Methylacrylate 1/1 90 do 1/1 90 (in 1/1 90 Q-KIU. do 111 90 7-K3AU.-- -do 1/1 90 B-AgKU--- .-.do 1/1 90 1-OzKU--- do 111 90 TABLE IX-A.-OLEFINA.TION

Schitfs base is present on the branched amino group rather than on the terminal amino group, etc.

(Carbonylation relates to the reaction of the branched polyamine and derivatives with aldehydes and ketones) Mols t OlefinIMol Branched oi Branched Poly- Temp., Example Polyamlne Olefin amine or Branched Time C.

Polyamine Derivative -U- N-800 Acrylonitrile 1 1 1 hr. 80-100 10-U:-- N-8 Styre 1:1 1 hr 80-100 10-115 N-800 Divinyl sulfone--- 1:1 1 hr 80-100 10-U N-800 Di-octylmaleate.-- 1:1 1 hr 125 ll-Ul N1200- Aerylonitrile 2:1 30 ml 80-100 ll-U: N-l200 Methylacrylate 1:1 30 min- 80-100 Ethyl erotonute--- 2:1 30 m1n 120 Divinyl sultone 2: 1 30 min 120 Ethyl cinnamate" 1:1 2 hrs.-- 120 Di-oetyl males-ten 1:1 2 hrs..- 120 Methyl meth- 1: 1 1 hr.... 100

acrylate.

Styrene 2:1 1 hr--- 100 Acrylonitrlle 2:1 1 hr 100 Ethyl I 1:1 1 hr- 110 Ethyl crot0nate 1: 1 2 hrs- 120 Dlvinyl sult'one--. 2:1 1 hr- 80 12-01HU. Lauryl meth- 3:1 2 hrs--. 130

' MIYIBW. 25111011111..- Acry onitrile 1:1 1 hr.. 00 16-K3HXU DivinylsullOnu--- 1:1 1 hr- 90 -K1U Styr 4:1 1 hr.. 90 33-ArO|KU 2:1 1 hr. 90 -A1OiHKU do 1:1 1 h.r- 90 CARBONYLATION A wide variety of aldehyde may be employed such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., inv eluding substituted derivatives such as those containing aryloxy, halogen, heterocyclic, amino, nitro, cyano,

W116i"e P y amino gfouPs am Pmsfillt 011 thc P Y' carboxyl, etc. groups thereof. Non-limiting examples are amine reactants, Schilfs bases can be formed on reaction with carbonyl compounds. For example, where an alde- Lesser molar ratios of aldehyde to polyamine would the following:

hyde such as salicylaldehyde is reacted with Polyamine Aldehyde-9 N-400 in a ratio of 3 moles of aldehyde to 1 mole of v polyamine, the following type of compound could be 40 Bmzaldehyde formed: 2-methylbenzaldehyde H H H H 3-methylbenzaldehyde C=N-(CH:CH1N)-GH:CHaN-CHaOH:NCHaCHsN=G 4-methylbenzald'ehyde (3H, Z-methoxybenzaldehyde 110 OH 4-methoxybenzaldehyde a-naphthaldehyde N b-naphthaldehyde 5 4-phenylbenza1dehyde Propionaldehyde HO n-Butyraldehyde Heptaldehyde Aldol Z-hydroxybenzaldehyd 2-hydroxy-6-methylbenzaldehyde yield monoor di- Schiffs base rather than a tri Schifls 5 Y Y- y y base such as H H H C=N(CH:CH:N CHaCHzN-CHrCHzNCHaCHzNHs 2-4-dihydroxybenzaldehyde 2-6dihydroxybenza1dehyde 2-hydroxynaphthaldehyde-l l-hydroxynaphthaldehyde-Z OH: HO (I311 AnthIo1-2-aldehyde-1 Z-hydroxyfluorene-aldehyde-l NH: 4-hydroxydiphenyl-aldehyde-3 H 3-hydroxyphenanthrene-aldehyde-4 3:1-(0H10H33)5:momtz-cmcnm-cmonmm ifi gs gfzfimg gsgzgg H0 2-hydroxy-3z5-dibromobenzaldehyde $11, 2-hydroxy-3-nitrobenzaldehyde 2-hydroxy-3-cyanobenzaldehyde 2-hydroxy-3-carboxybenzaldehyde 0-H 4-hydroxypyridine-a1dehyde-3 0H 4-hydroxyquinoline-aldehyde-3 7 -hydroxyquinoline-aldehyde-8 Formaldehyde Glyoxal and other isomeric configurations, such as where the Glyceraldehyde Schitfs bases are prepared with the polyamines of this invention in a conventional manner such as described in Synthetic Organic Chemistry" by Wagner and Zook (1953, Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be more complex wherein the carbonyl reactant instead of reacting intramolecularly in the case of Schifis base may react intermolecularly so as to act as a bridging means between two or more polyamino compounds, thus increasing the molecular weight of the polyamine as schematically shown below in the case where formaldehyde is the carbonyl compound:

In addition to increasing the molecular weight by means of aldehydes, these compounds result in the formation of cyclic compounds. 'Probably both molecular weight increase and cyclization occur during the reaction.

The following examples illustrate the reaction of car- 'bonyl compounds with branched polyamines. The symbol employed to designate carbonylation is C, acylation, carbonylation AC," and alkylation, carbonylation SKCJ Example I-C Charge 400 gramsof N400 and 400 grams of Xylene into a conventional glass resin apparatus fitted with a stirrer, thermometer and side-arm trap. Raise temperature to 120 C. and slowly add 122 grams of salicylalde- -hyde (1 mol). Hold at this temperature for 2 hours. Vacuum is then applied until all xylene is stripped otf. The reaction mass is a thick dark liquid which is soluble in water.

Example 6-C Using the same apparatus as above, charge 400 grams ture '82 grams of 37% aqueous formaldehyde (1 mol of HCHO). This reaction is exothermic and the temperature must be controlled with an ice bath. After the exothermic reaction has ceased, raise temperature to 100 C. The reaction mass may be stopped at this point. It is a viscous water-soluble material. However, it is possible to continue heating under vacuum until all of the water has been eliminated. Cross-linking occurs with this pro- Further examples of this reaction are summarized in the following table:

;; TABLE X.CARBONYLATION l Compound Aldehyde Moi. Temp., Time Ratio C.

1-01 Salicylaldehyde 1/1 120 2 hrs 1-C- do 2/1 120 2 hrs 1-0S do 3/1 120 2 hrs 2-01 2-hydroxy-3-methoxy- 1/1 130 4 hrs benzaldehyde. 2-01 do 2/1 130 4 hrs 3/1 130 4 hrs /1 130 4 hrs 1/1 110 1 hr. 2/1 110 1 hr. 3/1 110 1 hr. 3/1 90 2 hrs 3/1 130 5 hrs 3/1 2 hrs 2/1 100 1 hr. 2/1 135 3 hrs 2/1 150 1 hr. 1/1 120 2 hrs 1/1 120 2 hrS 1/1 120 2 hrs 2/1 120 2 hrs 1 Start 25 C., raise to 100 C.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

of N-400. While stirring, add slowly at room temperacedure and care must be taken to prevent insolubilization.

TABLE XA.CARBONYLATION Compound Branched Aldehyde M01. Temp., Time Polyamine Ratio C.

N800. Formaldehyde 2:1 lhour N-8o0 do 1:1 80 Do. 800 0.5:1 80 Do. 2:1 Do. 1:1 100 Do. do 0. 5:1 100 Do. Salicylaldehyde- 3:1 Do. do 2:1 120 Do. do 1:1 120 Do. Benzaldehyde.-- 3:1 110 Do. 18-A2O=C 2:1 110 Do. 31-A1O1C-. do 1:1 110 D0. 10O:AC Glyoxal 1:1 105 Do. 24O1AO d 0. 5:1 105 Do. 12O|HC d 0. 25:1 105 D0. Glyceraldehyde. 1:1 2hours o 0. 5:1 130 D0 d 1:1 80 1 hour 12-O1H UC do 0. 6:1 80 Do The examples presented above are non-limiting examples. It should be clearly understood that various otherlcombinations, order of reactions, reaction ratios, multiplicity of additions, etc. can be employed. Where additional reactive groups are stillpresent on the molecule, thereaction can be repeated with either the original reactant 01' another reactant.

The type of compound prepared is evident from the letters assigned to the examples. Thus, taking the branched polyamine as the starting material, the following example designations have the following meaning:

Example designation: Meaning (1) A Acylated.

(2) A0 Acylated, then oxyalkylated.

(3) AOA Acylated, then Oxyalkylated,

, then acrylated.

(4) AO-H Acylated, then Oxyalkylated,

then heat treated.

(5) AX Salt or quaternary of (1).

(6), AOX Salt or quaternary of (2).

(7) AOAX Salt or quaternary of (3).

(8) AOHX Salt or quaternary of (4).

(9) 0 Oxyalkylated. (10) 0A Oxyalkylated, then acylated. (11) OH Oxyalkylated, then heat treated. (12) K Alkylated. (13) KX Salt or quaternary of (12). (14) KA Alkylated, then acylated. (15) AK Acylated, then alkylated. (l6) AKX Salt or quaternary of. 15). (17) OK Oxyalkylated, then alkylated. (18) OKX Salt or quaternary of (17 (19) C Carbonylated. (20) AC Acylated, then carbonylated. (21) KC Alkylated, then carbonylated. (22) CO Carbonylated, then oxyalkylated. (23) U Olefinated. (24) AU Acylated, then olefinated. (25) KU Alkylated, then olefinated. (26) KUX Salt or quaternary of (25 USE AS A CHELATING AGENT This phase of the invention relates to the use of the compounds of our invention as chelating agents and to the chelates thus formed.

Chelation is a term applied to designate cycl-icstructures arising from the combination of metallic atoms with organic or inorganic molecules or ions. Chelates are very important industrially because one of the unusual features of the chelate ring compounds is their unusual stability in which respect they resemble the aromatic rings of organic chemistry. Because of the great afiinity of chelating compounds for metals and because of the great stability of the chelates they form, they are very important industrially.

The compositions of this invention are excellent chelating agents. They are particularly suitable for forming chelates of great stability with a wide variety of metals.

Chelating metals comprise magnesium, aluminum,

arsenic, antimony, chromium, iron, cobalt, nickel, palladium, and platinum. Particularly preferred of such metals as chelate constituents are iron, nickel, copper and cobalt.

The chelates formed from the compositions of our invention are useful as bactericidal and fungicidal agents, particularly in the case of the copper chelates. In addition the chelates can be employed to stabilize hydrocarbon oils against the deleterious effects of oxidation.

In general, these chelates are prepared by adding a sufii-. eient amount of a metal salt to combine with a compound of this invention. They are prepared by the general method described in detail by Hunter and Marriott in the Journal of the Chemical Society (London), 1937, 2000, which relates to the formation of chelates from metal ions and salicylidene imines.

The following examples are illustrative of the preparation of the chelates.

Example 8-A Q To a solution of 0.1 mole of the chelating agent of Example 8-A in alcohol is added 0.1 mole of cupric acetate monohydrate. After most of the alcohol is evaporated, a green solid precipitates which analysis indicates to be the copper chelate.

Example 6-K The above procedure is used except the cobaltous acetate tetrahydrate is employed to yield a red solid which analysis indicates to be the cobaltous chelate.

Example 4A C v The above procedure is used except that nickelous acetate, Ni(OAC) .4H O is employed. A dark green product 18 formed.

To save repetitive detail, chelates are formed from the above nickel, cobalt and copper salts, and the compounds shown in the following table.

CHELATING AGENTS USE IN EMULSION FLUIDS FOR DRILLING WELLS developed, is one of oil-in-water or water-in-oil emulsions, for example, emulsions of mineral oil in water or water in mineral oil formed by means of emulsifiers such as: sulfuric acid; Turkey-red oil; soaps of fatty acids, for example, sodium oleate; emulsoid colloids, for example starch, sodium alginate, etc. Varying amounts of finelydivided clay, silica, calcium carbonate, blown asphalt, and other materials may be added to these emulsions to improve their properties and control their weight.

The use of drilling emulsions has several advantages over the use of either water-base or oil-base drilling fluids.

Drilling emulsions are generally superior to water-base drilling fluids in forming a very thin substantially fluidimpervious medsheath on the walls of a borehole, in eliminating fluid loss to the formation and contamination of producing formations by an aqueous liquid, etc.

Drilling emulsions are generally superior to oil-base drilling fluids from the point of view of cost, of ease of handling, of suitability for electrical logging, etc.

The disadvantage for general use of drilling emulsions is, however, their lack of stability in the presence of even moderately high concentrations of electrolytes such as brines entering the borehole from the formation and becoming admixed to the drilling fluid.

Thus, drilling emulsions, formed by means of the emulsifiers listed above break down immediately or after a few hours of use or storage upon contamination with small concentrations of electrolytes, such as, for example, a 1% solution of sodium chloride. However, the present compounds provide an improved oil and water drilling emulsion or fluid which is substantially stable in the presence of contaminating formation salts or brines.

This phase of the present invention relates to drilling fluids of improved characteristics prepared by forming emulsions comprising oil, water, the compounds of this invention and, if desired various amounts of finely-divided clay, silica, calcium carbonate, and other materials to control the properties or weight of the drilling fluid.

Of the two general types of oil and water emulsion, i.e., oil-in-water and water-in-oil emulsions, the present invention is primarily concerned with oil-in-water emulsions where the oil is present in the dispersed phase while the water forms the continuous phase.

Various methods may be selectively used in forming well drilling emulsions by means of the agents of the present invention.

If it is desired to prepare a very light or low specific gravity drilling emulsion, a mineral oil, such as crude oil, gas oil, diesel oil, etc., is emulsified directly in water by means of a high speed hopper or a jet device, such as a so-called mud-gun, in the presence of a relatively small quantity, such as from 0.5 to 5% by weight or higher but preferably 2 to 3% by weight, based on the weight of 011 plus water, of the compounds of this invention. Depending on the specific gravity of the mineral oil, which should preferably be of a range from 10 to 40 A.P.I., and on the particular specific gravity of the drilling emulsion which it is thus desired to obtain for a particular purpose, -for example, for drilling through low pressure formations, the proportion in which oil is emulsified in water can be varied within fairly wide limits, although a ratio of about 25 to 50% by volume of the mineral oil to about 75 to 50% of water has been found to give especially favorable results.

Although in the above instances the present emulsions include only the three components described, that is, water, mineral oil and the emulsifying agent, various other components may be added thereto, if desired, for the purpose of controlling specific properties of the emulsions.

Thus, if it is desired to improve their plastering properties and thus to minimize the so-called filtering losses of the fluid to the formation, a blown asphalt can be added to the emulsion, and preferably to the mineral oil prior to emulsification, in relatively small quantities such as 33 from to 15% on the weight of the mineral oil, as described'in Patent No. 2,223,027.

If it is desired to give a greater consistency to the present emulsions and to increase their capacityfor carrying drill cuttings, a finely-divided solid and preferably a colloidal material can be admixed with the emulsions, preferably during the emulsification process, to form a stable three-phase emulsion. Thus bentonite may be added in, amounts of from 1 to 5% by weight, or ordinary drilling clay in amounts from 1 to 40% by weight on the total weight of the emulsion.

Furthermore, the weight or specific gravity of the present emulsions can be accurately controlled by adding thereto, in a suitably comminuted form, any desired weigh-ting material such as calcium carbonate, barytes, iron oxide, 'galena, etc. These materials have been found to remain stably suspended in the present emulsions while maintaining the specific gravity thereof within any desired range, such as from 67 to 120 lbs. per cubic foot.

Since the present emulsions are used on drilling installations wherein a drilling fluid of either the water-base or the oil-base type is usually already available, it has been found advantageous to apply the emulsifying agents of the present invention in forming drilling emulsions with these drilling fluids as starting material.

Thus, a water-base drilling fluid comprising water and clay and having a weight such, for example, as 86 lbs. per cubic foot, can be mixed with approximately 25 to 50% by volume of a heavy crude oil with the addition of 2.0 to 3.0% (calculated on the weight of the total mixture) of the instant compounds to give a stable emulsion having a weight of approximately 82 to 72 lbs. per cubic foot.

Likewise, an oil-base drilling fluid comprising, for example, crude oil or a diesel oil and calcium carbonate suspended the-rein by means of agents such as tall oil and sodium silicate or hydroxide, as described in Patent No. 2,350,154 and having a weight such, for example, as 78 lbs. per cubic foot, may be mixed with approximately from one to three times its volume of water and emulsified therewith with the addition of the instant compounds to give a stable emulsion having a weight of approximately 70 to 66 lbs. .per cubic foot.

In this connection, it is especially important to note that the emulsifying action of the present compounds is not in any way impaired by the chemical compounds which are ordinarily used in controlling the viscosity, stability or other properties of such water-base or oil-base drilling fluids.

The drilling emulsions formed in the Ways described hereina-bove have the following advantages over-waterbase and oil base drilling fluids; (1) they are considerably less expensive than oil base drilling fluids so that drilling costs are greatly decreased; (2) their plastering properties are much superior to those of water-base drilling fluids and compare favorably with those of oil-base drilling fluids so that filtering lossesv to the formation are greatly minimized; (3) they are better adapted than oil-base drilling fluids for surveying wells by electrical logging methods; (4) greater drilling speeds can in general be realized with the drilling emulsions of the present type than with either water-base or oil-base drilling fluids.

The following examples are presented to illustrate the present invention. 5

Example Drilling emulsions are prepared by emulsifying a Ventura clay water base drilling fluid, treated with 0.3% by weight of sodium hexametaphosphate and weighing about 75 lbs. per cubic foot, with stove oil in the weight ratio of 75% Ventura drilling fluid, 22% Stove Oil and 3% emulsifier. The emulsifiers employed in producing these emulsions are shown in the following table. These emulsions are useful as drilling fluids.

34 USE IN EMULSION FLUIDS FOR DRILLING WELLS Having thus described my invention, what we claim as new and desire to obtain by Letters Patent is:

1. A drilling fluid for wells containing an emulsion of water and oil, a fine dispersed solid weighting material dispersed in said emulsion, and a minor amount, sufficient to render the emulsion substantially stable in the presence of contaminating formation salts or brines,

of a compound selected from the group consisting of (l) a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula 1 NH: y

wherein R is an alkylene group having at least two carwherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24, y is an integer of 1 to 6, and z is an integer of -6, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polyalkyleuepolyamine with a compound selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, (3) an oxyalkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the a formula NH: y

wherein R is an alkylene group having at least two carbon atoms,

at is an integer of 4 to 24, y is an integer of 1 to 6, and z is an integer of 0-6,

- mula H NHr-(R-IL') r RNH:

l [is].

wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24, y is an integer of 1 to 6, and z is an integer of 0-6,

formed by reacting, at a temperature of from about 100 C. to about 250 C., said poly-alkylenepolyamine with a hydrocarbon halide alkylating agent having 1 to 30 carbon atoms, I

(5) an olefinated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula 36 wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by the reacting, at a temperature of from about 70 C. to about 100 C., said polyalkylenepolyamine with an olefinating agent selected from the group consisting of acryonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones,

(6) a Schifi base reaction product of a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary mino group and having the formula wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting said polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones,

(7) an acylated, then oxyalkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 125 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consistingof (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polyalkylenepolyamine, at a temperature of from about C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms,

(8) an oxyalkylated, then acylated branched polyalkylenepolyamine, containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 psi. to about 200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least 2 carbon atoms and then reacting said oxyalkylated polyalkylenepolyamine, at a temperature of from about 120 C. to about 300 C., with an acylating agent selected from the group consisting of (i) -a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction,

(9) an alkylated, then acylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about C. to about 250 C., said polyalkylenepolyamine with a a hydrocarbon halide alkylating agent having 1-30 carbon atoms, and then reacting said alkylated polyalkylenepolyamine, at a temperature of from about C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a prethen reacting said acylated polyalkylenepolyamine,

at a temperature of from about 100 C. to about 250 C., with a hydrocarbon halide alkyl-ating agent having 1-30 carbon atoms,

(11) an oxyalkylated, then alkylated branched polyalkylenepolyamine containing at least three primary 38 then reacting said acylated polyalkylenepolyamine, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones, and (16) an alkylated, then olefinated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having from 1-30 carbon atoms, and then reacting said alkylated polyalkylenepolyamine, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

2. The drilling fluid of claim 1 wherein the compound is a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula NH: y

amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed 20 by reacting, at a temperature of from about 80 C. to about 200 C., and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least 2 carbon atoms, and then reacting said oxyalkylated polyalkylenepolyamine, at a temperature of from about 100 C. to about 250 C., with a hydrocarbon halide alkylating agent having lcarbon atoms, 1

(12) a Schiif base reaction product of an acylated branched polyalkylenepolyamine containing at least 30 three primary amino groups and at least one tertiary amino groupand having the hereinabove recited formula, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones,

(13) a Schiff base reaction product of an alkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited for.- mula, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having 1-30 carbon atoms, and then reacting said alkylated polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones,

(14) an oxyalkylated Sehiff base reaction product of a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary 5 amino group and having the hereinabove recited formula, formed by reacting said polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones to form said Schili base reaction product and then reacting said Schilf base reaction product, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 psi. to about 200 psi, with an alkylene oxide having at least 2 carbon atoms,

(15) an acylated, then olefinated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consisting of (i) a earboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and NH: y

RNlh

wherein R is an alkylene group having at least two carbon atoms, 35 x is an integer of 4 to 24,

y is an integer of l to 6, and

z is an integer of 0-6.

3. The drilling fluid of claim 1 wherein the compound is an acylated branched polyalkylenepolyamine contain- 40 ing at least three primary amino groups and at least one tertiary amino group and having the formula l NH: y.

w RNII2 wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24,

y-is an integer of 1 to 6, and

z is an integer of 0'6,

formed by reacting, at a temperature of from about C. to about 300 C., said polyalkylenepolyamine with a compound selected from the group consisting of 60 (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction. 4. The drilling fluid of claim 1 wherein the compound is an oxyalkylated branched polyalkylenepolyamine con- 65 taining at least three primary amino groups and at least one tertiary amino group and having the formula 39 wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24, y is an integer of 1 to 6, and

z isan integer of -6,

formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about p.s.i. to about 200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least two carbon atoms.

5. The drilling fluid of claim 1 wherein the compound is an alkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having theformula RNH:

wherein r RN 1min I NH:

wherein Y R is an alkylene group having at least'two carbon atoms,

x is an integer of 4 to 24, y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting, at a temperature of from about 70 C. to about 100 C., said polyalkylenepolyamine with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

7. The drilling fluid of claim 1 wherein the compound 6 is a SchiflE base reaction product of a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24,

' y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting said polyalkylenepolyami-ne with a compound selected from the group consisting of aldehydes and ketones. I

8. The drilling fluid of claim 1 wherein the compound is an acylated, then oxyalkylated branched polyalkylenepolyamine containing at least three primary amino groups 'and' at least one tertiary amino group and having the I NH:

RNH:

wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6,

formed by reacting, at a temperature of from about 125 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polyalkylenepolyamine, at a temperature of from about C.

to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,243,329 5/1941 De Groote et a1 252-344 2,272,489 2/ 1942 Ulrich. 2,403,960 7/1946 Stoops et al 260404.5 2,802,531 8/ 1957 Cardwell et a1. 2,946,746 7/ 1960 Keller. 2,999,063 9/ 1961 Hoeppel. 3,060,210 10/1962 De Groote et al. 3,133,941 5/1964 Edwards et al 252-392 FOREIGN PATENTS 233,766 5 1961 Australia.

ALBERT "r. MEYERS, Primary Examiner.

JULIUS GREENWALD, Examiner.

H. B. GUYNN, Assistant Examiner. 

1. A DRILLING FLUID FOR WELLS CONTAINING AN EMULSION OF WATER AND OIL, A FINE DISPERSED SOLID WEIGHTING MATERIAL DISPERSED IN SAID EMULSION, AND A MINOR AMOUNT, SUFFICIENT TO RENDER THE EMULSION SUBSTANTIALLY STABLE IN THE PRESENCE OF CONTAMINATING FORMATION SALTS OF BRINES, OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA 